DE2262340A1 - STYLE CONNECTIONS - Google Patents

Description

Polentor.wfilfe

Dipl.-I.ici. P. Wirth

Dr. V. Sviimd-Kov / arzik

Dipi. | .-. g. G. Djnr.orsbcvg

Df. P. Weii & oH, Dr. D. Gudel

Frankfurt / M., Gr. Eschenheimer. St.

SANDOZ A.G. Basel, Switzerland

Case 1

S111 he πνοrb1 ndungen

The invention relates to new stilbene compounds of the formula

CH = CH-

q-I

wherein each of the symbols R, and Rg. Hydrogen, nitrile or 1-4 carbon

linear alkyl containing lenstoffatonie ^

each of the symbols R _p , R ₂ ^, R ^. and 'R' hydrogen, one of the following

1st order substituents: halogen, containing 1-3 carbon atoms

309826/1193

- 2 - - Case

Alkyl or alkoxy or alkenyl containing carbon atoms or one of the following 2nd order substituents: -CN, -COOK ¹ , -CONR'R ", -SO ^ R '", -SO ₂ NR ¹ R "or SOgR"",

each of the symbols R and R “hydrogen, one of the substituents mentioned 1st or 2nd order or one of the heterocycles of the following formulas

R 'is hydrogen, alkyl containing 1-22 carbon atoms, hydroxyalkyl containing 2-4 carbon atoms or, if applicable: optionally methyl- or chlorine-substituted phenyl,
R "is hydrogen, alkyl containing 1-8 carbon atoms or hydroxyalkyl containing 2-4 carbon atoms,

or R "and R ^? together with the adjacent nitrogen atom form one

Pyrrolidine, piperidine, piperazine or morpholine,
R ^IM optionally methyl- or chlorine-substituted

Phenyl,

R ¹ " ¹ 1-4 carbon atoms containing alkyl or contr

optionally methyl- or chlorine-substituted phenyl,

9826/1198

ORIGINAL INSPECTED

Case

X -0-, tS -.- NH- or -NR "'" -,

R " ^{l! T} alkyl containing 1-4 carbon atoms or 2-4

Hydroxyalkyl containing carbon atoms,

A ₁ and Ap when X is -0-, optionally by chlorine or

1-4 carbon atoms containing alkyl or alkoxy substituted phenyl or, if X denotes -0-, -S- or -NR " ^m -, a fused naphthalene nucleus or a fused, optionally by fluorine, chlorine, nitrile, 1-8 Alkyl and / or alkoxy-substituted benzene ring containing carbon atoms,

A, optionally by one of the abovementioned substituents 1,. Order or non-heterocyclic substituents of the 2nd order substituted phenyl, A;, hydrogen or methyl,

ρ is an integer from 1 to 3

and q is an integer from 1 to ^, the sum piq is at least 3, the sum of p + q and the number of substituents present in the molecule is 2, order at least 5, the heterocycles (a), (b) and (c) also to the substituents 2-. Order count, and -CN as substituents2. Order for R ₁ and R _r applies, and, if only one of the substituents R 1 and R is a heterocycle, either the sum p + q is at least 4 or / and at least two other non-heterocyclic ones. there are substituents 2 »order in the molecule *

...... 309826/1198 '

Depending on the meaning of the symbols ρ or q,
one group on each side of the middle "-CH = CH-" group
be bonded from one, two or three aromatic rings »where the substituent R, - or R ^ is in the codein case in the ortho position to the -CH = CH- group, while the substituents Rp to R ^ or Rg to Rq at the outermost
Phenyl radical are bound.

The compounds of the formula (I) can be prepared by processes known per se, for example by forming the ethylene double bond of the stilbene or by converting the substituents of a Molkül already having the basic structure of the compounds of the formula (i) into substituents under the
the above definition of formula (I) fall; furthermore, substituents in the compounds of the formula (i) can be converted into other substituents falling under this definition.

309826/1198

In detail, compounds of the formula (I) can be prepared by making a compound of the formula. '

(II),

p-1

wherein Y -GO-COOH or -CHO or a suitable functional De derivative of the aldehyde group means with a compound of the formula F.

(in),

wherein Z is a substituent which activates the adjacent methylene group or, when Y is an amine derivative of the aldehyde group and if no equally active or more active methyl is present is, also means hydrogen, converts and, if in the reaction product a substituent Z other than hydrogen is present, replacing it with hydrogen, or by adding -'-

30 9 8 2-6 / 1 198

Case 150-3352

fertilize the formula

v ^)> - © - ^c <* iV ^R 4

(IV),

wherein each of the symbols Y and each of the symbols Z, hydrogen, halogen, a hydroxy or acyloxy group or (Y,) p and / or (Z *) _p each represent double oxygen, two of the substituents Y, and Z. optionally with simultaneous reduction or oxidation, and if Y and / or Z substituents other than H are still present, these are replaced by H or, if at least one nitride group is present in the compounds of formula (I) by 'man.in a compound of the formula

p-1

in which at least one of the symbols R ¹ to R ^1. , is halogen and the remaining symbols are in formula (I) corresponding ■■ .-. . for R ^ - to Rg specified terms; have, dos halogen through -CN

Ά 0 9 8 ? B / 1 1 9 8

BATH ORIGINAL

- € -

Case 150-3552

replaced, or by in the compounds of formula (i), wherein

R ₇ or Rq for

at least one of the substituents Rp, FL, R ₂ ,, -CN is the latter to a corresponding carboxamide, carboxylic acid ester or free carboxylic acid group, or by converting into compounds of the formula (I.) wherein at least ¹ of the substituents R, and R _{7 are} Carboxylic acid, carboxylic ester or carboxylic acid amide group means, if appropriate after conversion to a corresponding carboxylic acid halide group, this group converts to a corresponding heterocycle (a). ...

Symmetrical compounds of the formula (I) can also be prepared ^ by making a compound of the formula

1 (5)

where W is hydrogen, halogen or -P (aryl)., Äniön ^ and aryl is preferably mononuclear (optionally substituted phenyl) reacts in an alkaline medium and / or under oxidative conditions, where, if W is halogen, the medium must be alkaline , if W stands for hydrogen, one must proceed in the presence of an oxidizing agent and if W stands for [P- (A-FyI) -J ^ anion, one must proceed in the presence of a proton acceptor and an oxidizing agent, or alternatively ^one must use symmetrical compounds of the formula ■ ■

ψ- *

Case 13O-335

R '

O-CO-CH = CH-CO-O

ρ-1

(VII)

or the formula

H = N-N = CH

ρ-1

.-1

by thermal treatment in an inert gas atmosphere CO or Np splits off.

The intermediate products of the formula (V),

can according to methods known per se

can be produced, e.g. analogous to the methods described above, by reacting compounds of the formula

with compounds of the formula

30982G / 1198

Case

z-cB

(X)

-J q-l

or of compounds of the formula

c (Y ₁ ) ₂ -c (z ₁ ) ₂

or [for symmetrical compounds of the formula (V)] of the formula

or the formula

1 (5)

p (<j V-I

(XU)

R ¹ .

R ¹

O-CO- CHr = CH-CO-O-

or the formula

p-1

309826/1198

(SIII)

Case

p-l

(XIV)

Furthermore, the Zv / ischen.produkte of the formula (V) by reaction of compounds of the formula

(XV)

with ilalogenacetaldehyde or its functional derivatives and an- ' NS! 1 Eating dohydrohalic reduction rubbed rearrangement of the reaction; - Product has been manufactured.

As in the compounds of formula (I) occurring 'alkyl radicals (sub-substituents of the 1st order) selenium, for example, the following are mentioned: - methyl, ae thy I, n-propyl, iso-pronyl, η-butyl,!.' Jo- Butyl, tortriiutyl, ni-aniyl, tor tr amyl, iiSO-amyl, sec.amyl, n-hexyl, n-octyl, iyo-octyl and 2-ethyl-hexyl, where the alkyl rusts R and R _{r are} only linear with 1-Λ carbon atoms come into question, ie methyl, ethyl, n-propyl and η-butyl. In general, the nLedrigr: in] ekularon (l -: ^. Coals:; toff · atoms) are preferred, while for R and R _r, methyl is preferred. As alkenyl and Alko.xygruppen (1st order sub-substituents) the following are mentioned, for example: allyl, 1-, 2- or> -butenyl, 1-hexenyl, methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy, n-IIcxyloxy or

309826/1198

2-Aethylhexyloxy, of which the 1-4 carbon atoms contain Alkoxy radicals, especially methoxy, are preferred.

In the compounds of the formula (I), there are in particular halogen atoms Fluorine and preferably chlorine atoms into consideration ^ during as reactive halogen atoms in the intermediates mainly Chlorine, bromine and optionally iodine atoms are suitable come. -

As "non-heterocyclic" substituents of the 2nd order, i.e. substituents 2nd order with the exception of the heterocycles (a), (b) and (c), for example the following are mentioned: the Nitri! group »the Carboxyl group, carboxylic acid alkyl ester in which the alkyl radical contains 1-22, preferably 1-8 carbon atoms, e.g. carboxylic acid ethyl-, -ethyl-, -propyl-, -iso ~ propyi-, -butyl-, -amyl-, -hexyl-, -isooctyl-, -n-decyl-, .- n-dodecyl-, -cetyl-, - stearyl ester groups, also the carboxylic acid ~ / 3-hydroxyethyl, -ß-hydrOxypropyl-, -phenyl-, -p-chlorophenyl-, - p-methylphenyl-, -2,, 4-dimethylphenyl or -2,5-dlchlorophenyl ester groups, Sulphonic acid phenyl-, -p-chlorophenyl-i ^^ - dichlQrphenyl-, -p ~ methy! phenyl or -2,4-dimethylphenyl ester groups, methyl, Ethyl, n-propyl, iso-propyl, η-butyl, iso-butyl, tert-butyl, Phenyl, p-chlorophenyl, p-methylphenyl, 2,4-dimethylphenyl or 2,4,6-trimethylphenylsulfone groups, the free carboxylic or sulfonic acid amide groups or the carboxylic or sulfonic acid amide groups, the.-a.D. derived from the following amines: Methyl ·, Aethyl-, Prspyl- ^ Butyl-, tertr-butyl- ,. Amyl, iso-amyl, hexyl, octyl, lauryl ._ Dimethyl-, diethyl-ethanol- or diethanolamine, N-methyl-N-ethylamine, N-methyl-N-propylamine, aniline, toluene, xylidine,

£ 8 26 ^ 1 WS . ..... '' ■■ - ■■■ -

- ** "- Case 150-3352

p-chloroaniline or N-methylaniline, pyrrolidine, piperidine, piperezin or morpholine. Among the mentioned Suöstituenten 2nd order are the following preferred:

-CN, the alkyl sulfone groups, -SO ₂ -C ₀ H ₅ , -SO ₃ -C ₆ H ₅ , -CONHg, -CO-NHCH ₅ ,

-CO-N (CH,) ₂ , -CO-N (C ₂ H) ₂ , -CO-N (CH ₂ CH ₂ OH), -CG-NH-CHgCHgOH, the carboxylic acid alkylsber groups (preferably contains alkyl I,

2, 3 or 4 carbon atoms), - SO ₂ NH ₂ , -SO ₂ NHCH ₃ , -S0 ₂ N (CH ₃ ) ₂ and -SO ₂ NHC ₆ H ₅ .

For the substituents R 1 and R ₇ , the heterocyclic substituents of the 2nd order of the formulas (a), (b) and (c) can also be used in addition to the specified substituents.

In the remainder of the formula (a), X stands for sulfur, imina, alkyl- or hydroxyalkylimino, where alkyl contains 1-4 carbon atoms and hydroxyalkyl contains 2-4 carbon atoms (methyl, ethyl, n-propyl, · isorPropyl-, n-butyl-, tert-butyl-, p-hydroxyethyl- or ß-hydroxypropylimino) or preferably for oxygen. If X is oxygen, then Λ 'and A can each have the following meanings, for example: Phenyl, 4-methyl, 2,4-dimethyl, 3 ^ -dimethyl, 4-ethyl, 4-butyl-> 4-kethoxy-, l ~ / \ ethoxy- or 5-methyl-4-niethoxyphenyl. If A, and Ap together form a condensed ring, this is an unsubstituted one Naphthalene ring or a benzene ring, preferably in one or optionally each of positions 5 and 6 of the benz-X-azole ring preferably one of the following substituents: methyl, ethyli n-propyl, η-butyl, methoxy-ethoxy, n-butoxy, tert-rutoxy, Chlorine, or -CN can carry.

The remainder Λ-, both unsubstituted and arbitrary

309826/1198

Case 150-3352

phenyl substituted by the abovementioned substituents of the 1st order or non.heterocyclic substituents of the 2nd order. A 1, ⁵ is preferably phenyl or p-chi or phenyl.

The sum p + q can be 3 to 6, which are particularly preferred however, compounds of the formula (I) in which p + ^. 4 »5 or 6 is l In particular, the following compounds should be mentioned because of their good properties as optical brighteners. The compounds of the formula

wherein each of the symbols each of the

CH = CH

PI

2_- and R ₁ C hydrogen, methyl or -CN, hydrogen or -CN,

Symbols R, ^, and R hydrogen or one not

2nd order heterocyclic substituents, preferably -CN, an alkyl or phenylsulfone group ^v or a carboxamide or ester group and each of the symbols R _o , Rl, Rx- and Rq is a substituent

1st order or preferably hydrogen

means, the molecule containing 2 to 4 substituents of the 2nd order.

The compounds of the formula

303826/1198

21

-Jr-I

C as'c

CH = CrI

(XVII) ₁

wherein R ^ and R are hydrogen, methyl or cyano, preferably

Hydrogen or cyan,

R "~, R" i., R ,,, r and R ^ _{0 are} hydrogen or a substituent 1. Orel-22 24 Zb 28

tion, preferably hydrogen, R ₀ -. and R in each case one of the heterocyclic substituents 2, order of the formula (a), (b) or (c),

r is an integer from 1 to 3j, preferably 1 or 2 and. s is an integer from 1 to 3, preferably 1 or 2, and the sum r + s is 3 or k .

The compounds of the formula

(XVIII),

wherein R and R are hydrogen, -CN or methyl, preferably -CN

or methyl,
R -., -., R., 2 ,, R. c and R ₇ ^ hydrogen or a substituent!, Order,

for example hydrogen,

one of the symbols R and R one of the heterocycles (a), (b) and (q),

3098 2 6/1198

. Case ljp-5352

ν ■

the other of the symbols R and R _ hydrogen, a substituent

1st order or a non-heterocyclic - -. 2nd order substituents,

t is an integer from 1 to 3 "~~ - ■

and u is an integer from 1 to 3 '

mean, where the sum t-fu 3 * ^ Qder is 5, at least one the -Substituenten R -, - ,, R ,, - and R___ or R -, .. a non-heterocyclic

31 35-33 '3i ■

shear structural element is of the 2nd order and, if the sum t + u is 3, at least two of the substituents R. ,,, R. ,,. and R___ or R_ "not

. . 3 ¹ 35. 33 37

2nd order heterocyclic substituents.

What is essential, especially the good properties as optical brighteners, of the compounds of the formula (I) is the combination between the basic structure and the 2nd order substituents and their position in the molecule. The compounds with the best properties are those in which at least one, but also two, three or all four of the substituents R ₁ , R-, R ₁ - and R are substituents of the 2nd order. The first-order substituents per se have no significant influence on the actual brightener properties, but can ZcB. the solubility in organic polymers.

■ affect ,. Even if the substituent R _? , R.,

R ^ and R ₀ substituents of the 2nd order are present in the molecule, so ο ο

have these, compared to substituents. 2nd order R, R, R and R ₇ , no significant influence on the fluorescence of the brightener or a substrate brightened with it. Thus, in general, the compounds of formula (I) are in which R ", Rj, j R <; and Rg denote hydrogen, compared to those in which Rp, R ^ Rg and Rp of water

3OS826 / 11

Case 150-3352

Hydrogen are different, preferred.

In the compounds of the formulas (II) and (IX), Y is one of the Groups -CO-COOH or -CHO or a suitable one for the implementation functional s derivative of the aldehyde group, ζ.-B, an AhJ 1 «a hydrazone ,, an oxime or an azine. In the compounds of the formulas (III) and * (X) Z denotes hydrogen or a residue of the CtU group in such a way activated that they with the aldehyde, or «'its derivative, or can be reacted with the ketocarboxylic acid group. Such act * - Fourth groups are, for example, the carboxyl group, a carboxylic acid ester- ^ or amide group, optionally the cyano group, and particularly advantageously one of the groups

• Q-aryl> 4K

PO

0-aryl ^ aryl

O-alkyl / Q-alkyl

or -tP (aryl) -,] ® anion ^

where alkyl is preferably of low molecular weight (zui. »it I bta 6 Carbon atoms) and optionally is (e.g. by methoxy, ethoxy> and also cycloalkyl (e.g., cyclohexyl)

Aryl preferably mononuclear (given case

Phenyl) is * and anion © is an equivalent Rfc eimtea any suitable anion «, preferably a mineral acid Z« Ö. Ql ■ or Br ".

309826/1198

'■■ Case 150-3352

The reaction of a compound of the formula (II) with a compound of the formula (ΙΙΪ), or the reaction of a compound of the formula (IX) with a compound of the formula (X) takes place according to methods known per se, for example with exclusion of air and advantageously in Ge ^ genwart of a suitable catalyst such as boric acid, zinc chloride, aryl sulfonic acids, alkali metal or alkaline earth salts of aryl sulfonamides, acetic anhydride, alkali metal acetates, piperidine, alkali or alkaline earth, alkali metal or alkaline earth metal practical 'at temperatures of from 0 ° to 200 ⁰ C, preferably from 20 ° to 160 ° Cj if a radical Z other than hydrogen is present in the reaction product, this is replaced by H in a suitable manner. The reaction can be carried out, for example, by melting the reactants together, but advantageously in an inert solvent, for example in aliphatic or aromatic, preferably halogenated, hydrocarbons, alcohols, ethers, glycols or formamide, dimethylformamide or acetamide, N-methylpyrrolidone, acetonitrile, dimethyl sulfoxide, tetramethylene sulf on or Hexarnethylphosphors'äuretriamid be carried out. For the implementation of phosphorus-containing compounds (. Wittlg synthesis and similar reactions) see-for example also "Organo-Phoshorus Compounds", International Symposium, Heidelberg (196 ^) "Butterworth's Scientific Publications. ■

The ünsetzuigen the compounds of formula (IV) or of formula (XI) be carried out by known methods, as may, for example the dehydrogenation of the compounds in which all radicals Y ₁ and Z ₁ is hydrogen, to the corresponding stilbene compounds analogous to the mode of operation described in DOS 1 670 398, for example

3098 26/1198

Case 150-3352

as indicated below, were carried out ¹ ^ r :. If one or more of the symbols Y and Z ₁ denote halogen (preferably chlorine or bromine) and optionally the remaining symbols Y ₁ and / or Z denote hydrogen, dehydrohalogenation is carried out in a manner known per se, expediently in the heat , preferably at temperatures between 100 and 300 °, in particular between I50 and 200 ⁰ C in the presence of higher boiling alcohols or glycols (ethylene glycol, propylene glycol) and / or of strong bases (alkali alcoholates); dehalogenation is also carried out according to methods known per se, for example with metals (e.g. zinc) or with copper (I) compounds or with triarylphosphines in polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, etc., in the heat, preferably at Reflux temperature; Acyl-OH is split off analogously to dehydrohalogenation, acyl-OH preferably denoting a low molecular weight, easily split off acid, such as benzoic acid or, preferably, acetic acid. Compounds in which two oxygen atoms are present in the bridge member -C (Y ^ -CvZ,) ^ .--, optionally, except hydrogen, preferably benzoin compounds can be directly reduced to the corresponding stilbene v / ground, for example with Zn Araalgam H and _O / HC1 stream in boiling alcohol [cf. for example Baroni, CA. 5 £, 15'-Oe and Journal für Practical Chemistry, 4th series, Volume 20 (19 * 53) pages ¹ Jo-Ol]. Although this reaction is also suitable for the preparation of asymmetrical compounds, symmetrical compounds of the formula (I) are preferably prepared in this way, since, as is known, benzoin compounds can easily be prepared from the corresponding aldehydes.

3098 26/1198

226234Ö

- "β" case

The compounds of the formulas (IV} or (Xl), wherein at least one the substituents Y and Z- are halogen, preferably bromine can be prepared analogously to known methods, see e.g.

j. former

The replacement of a halogen (preferably bromine) by a nitrile group in the compounds of the formula (V) takes place in a generally known manner. Way z :. _; B. by reaction in a: suitable polar, organic solvent, for example in one of the solvents listed above. Chlnxxlin, Quinaldin and / or Alkylpyriäinen (z * B. Lutidln) with a suitable cyanide ,. preferably CuCN, optionally mixed with alkali or alkaline earth cyanides »

The conversion of a nitrile group into a corresponding carboxylic acid., Carboxamide or Carbonsäureestergruppe 1st a common Faoiimann the implementation and done, for example lh presence of water and / or alcohol and alkali or mineral acid in the heat ·

The conversion of a carboxylic ester or halogen group (R or E ₇ ) to an X-azole ring (a) takes place according to methods known per se, for example by reaction; with a compound of the formula

where preferably A ₁ and A "together form a condensed aromatic king"

If the end product of the formula (I) contains heterocyclic substituents J * and / or R ", however," substaiizen "are preferably used * ^ s *. V «(^ C already received ^ ccyeleri.

BATHROOM ORIGINAL,

C ^ se 150- '

to

The reaction of compounds of the formula (VI) or (XII) takes place by methods known per se, for example as described in the following.

If W is hydrogen, the reaction takes place in the presence an oxidizing agent, in particular oxygen or sulfur.

If the procedure is carried out in the counterv / kind of oxygen, one can proceed analogously to the procedure described in DOS I67O 398, namely in a polar neutral to basic solvent, preferably a dialkylated acylamide, in particular dimethylformamide, diethylformamide, dimethylacetamide and hexamethylphosphoric triamide, whereby one advantageously in the presence of a strongly basic alkali metal compound, preferably an alkali metal hydroxide, alkoxide or amide, and using, where appropriate, mixed with inert gases oxygen, for example in the form of air and advantageously at temperatures between 10 ° and 15O ⁰ C, preferably between 30 and 100 ⁰ C operates. When using this working mode, it is necessary

ι borrowed that the starting substances of the formulas (VI) or (XIl) do not contain any atoms which can be replaced by alkali metal. In the use of sulfur as an oxidant, the procedure is advantageously carried out at temperatures between 200 and 35O ° C, preferably between? 50 and 300 ⁰ C, in the absence of solvents, in which to use the s.töehiometrische amount Schwefel.oder also an excess of sulfur can.

The implementation of the compounds of formulas (VI) or (XII) in which W stands for a halogen atom, preferably chlorine or bromine »he *.

followed with strong bases (e.g. alkali and / or alkaline earth hydroxide,

3Q9826./119.8.

- Se- - ~ - Caje 150-3352

alcoholate or amide, in particular KOH, potassium tert-butylate or NaNH ₀ ) advantageously in a polar solvent such as dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, alcohol, etc. 'in the heat, for example - depending on the solvent - between 60 and. 200 °, preferably at reflux temperature. '.- .. "

A modification of the above oxidation process with oxygen or sulfur is that instead of the compounds of the formulas (VI) or (XII) in which W is hydrogen, those in which W is -P (aryl), anion, are used, in which aryl is preferably mononuclear (optionally substituted. Phenyl) and AnicrF * has the meaning given above and z-.B. analogous to that in Chem.Ber. 103, 2995-2997 (1970) described procedure proceeds. Another approach is that it connects ¹ fertilize the Formein (VI) or (XII), are used in which W -P means. (Aryl), anion ", wherein at least one of the anions oxidizing properties and is used as the oxidizing agent is Periodates are preferably used. The reaction is carried out, for example, analogously to the manner described in DOS 1 925 255 with anhydrous bases, in particular with alkali and alkaline earth metal alcoholates in dry alcohol, under warm conditions, preferably at reflux temperature.

The pyrolytic reactions of the fumaric acid esters of the formulas (VII) or (XIII) and the aldazines of the formulas (VIII) or (XIV) are also carried out by methods known per se, in particular under an inert gas atmosphere, optionally in the presence of a high-boiling solvent such as Dowtherm or solvent naphtha , advantageously at temperatures between 200 and 400 ^u C, preferably at about

The dehydrohalogenation and possibly simultaneous rearrangement

309826/1198

- - dft - ■ -ChSL ¹ : · 50-3352

ung the reaction products of compounds of the formula (XV) (preferably those in which R ', "" is different from hydrogen) with Haloacetaldehyde takes place according to methods known per se, for example as indicated above for the compounds of the formula (XI).

The starting compounds of the formulas (II), (III), (VI), (IX), (X), (XII) and (XV) can be prepared by known methods or analogously to known methods. The compounds of the formulas (IV), (VII), (VIII), (XI), (XIII) and (XIV) can be prepared analogously to known methods, e.g. by reacting hydrazine with the corresponding aldehydes to compounds of the formulas (VIII) and

ι ¹

(XIV), or by reaction of fumaric acid or a suitable one functional derivative thereof with the corresponding phenols to form compounds of formula (VII) and (XIII), or as, for example, given above for the compounds of formulas (IV) and (XI).

The compounds of the formula (I) prepared as indicated above can by redissolving from an organic solvent, if appropriate with the addition of decolorizing charcoal or lead: stoves, cleaned will. Some of them have a relatively low inherent color and are not very soluble in water. In organic solvents such as chlorobenzene, ortho-dichlorobenzene, dimethylformamide or -acetamide, or 2-ethoxyethanol, they dissolve, however, with production intense purple to blue fluorescence.

The compounds of the formula (I) have excellent properties as optical brighteners and are suitable for the optical brightening of the most varied of textile and non-textile substrates mainly from natural and synthetic organic polymers. Natural organic polymers are, in particular, fiber materials

309826/1198:

BATH ORIGINAL

. Case 150-3352 such as cotton, linen, wool, and silk. Synthetic, especially fiber-forming polymers are e.g. polyesters, polyamides, polyurethanes, polyolefins (polyethylene, possibly modified polypropylene), Polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, modified polyacrylonitrile, cellulose triacetate, cellulose-2 1/2 acetate and polystyrene ..

The compounds of the formula (I) can be used in the customary manner as optical brighteners, for example in the form of solutions or as suspensions in organic solvents or as aqueous dispersions. Above all, however, they are incorporated into spinning and molding compounds with good success or added to the monomers intended for the production of plastics, or to a precondensate of the same. The compounds of the formula (I) according to the invention are particularly suitable as spinning mass whiteners for polyesters. The concentration of the brightener can be, depending on the application process, for example Qj-OOl up to 0.5 % _}, preferably 0.01-0.2 %, of the compounds mentioned, based on the material to be brightened. The compounds of the formula (I) can be used alone or in combination with other brighteners, and in the presence of finishing agents (eg plasticizers, antistatic agents, finishing agents), of surface-active agents such as V / a schmittein or carrier η or in the presence of chemical bleaching agents. . ·

In the following examples, the percentages mean percentages by weight and the parts, unless otherwise specified, are by weight; the Parts by volume stand for parts by weight as ml to gr; the temperatures are given in degrees Celsius; the melting points -are, .unkpr- ..

309826/1198 .;

example 1

tv

Preparation of the compound of formula

fse 150-3352

(1)

Method a

Parts of the compound of the formula

(2)

and 72.6 parts of copper (I) cyanide in 100 parts by volume of dimethylformamide are refluxed with stirring for 4 hours.
The reaction mixture is then concentrated in a solution of 28.5.0 parts of iron (III) chloride in 71 parts by volume. Hydrochloric acid and k2 ^l j parts of water \ poured inter stirring and further stirred for 20 minutes at o0-70 ° "The suspension is subsequently cooled, the precipitate filtered off, washed with water and dried. After recrystallization from dilute methanol, the compound of the formula is obtained in good yield

(3)

with a melting point of 110-111 °.

97.5 parts of the compound of formula (3), 90.0 parts of N ^ bromosuccinimide and 1.1 parts of benzoyl peroxide in 505 parts by volume of carbon tetrachloride are refluxed for 18 hours with stirring

309826/1198

C & se 1 ^ 01

cooks. The reaction mixture is then cooled and the Sucked off precipitate. The filtrate is concentrated strongly in vacuo , then cooled and sucked off the precipitated product, with Water washed and dried. By recrystallization from ligro-

in the compound of the formula is obtained in very good yield

CH ₂ Br (4)

with a melting point of 106-107 °.

82.1 parts of the compound of formula (4), and 79.1 parts of triphenylphosphine in 2000 parts by volume of toluene are refluxed for 2 hours with stirring and with exclusion of moisture. The mixture is then cooled and the precipitate is filtered off with suction and dried. The is obtained in practically quantitative yield Compound of formula. - - "■

which is implemented further without additional cleaning.

52.2 parts of the compound of the formula (5) are dissolved in 4000 parts of hot water with stirring, with a solution of 21.2 parts Sodium periodate in 200 parts of water is added rapidly, 10 minutes still stirred, then cooled, the precipitate filtered off with suction and dried. The compound of the

Formula.

309826/1198

Case 150-3352

which is implemented as follows:

75.0 parts of the compound of formula (6) in 900 parts by volume of absolute ethyl alcohol are slowly added with stirring at 60 ° with a solution of 9/3 parts of sodium ethylate in 290 parts by volume of absolute ethyl alcohol. The mixture is then refluxed for ~ 1 hours, then cooled, the precipitate is filtered off with suction, washed with water and dried. After recrystallization from chlorobenzene with the addition of fuller's earth, the compound of formula (1) is obtained with a melting point of 252-255 °.

Method b

One is to 6O-65 ⁰ heated clear solution of 2 NC, 7 parts of the phosphonium salt of formula (5) in parts of dimethylformamide 6OO "-having nitrogen and exclusion of moisture over 15 minutes with a freshly prepared solution of 1.5 parts of sodium in JO parts The deep orange-red suspension is stirred for a further 30 minutes at 80 ° and then evaporated to dryness in a waterpump vacuum at 50 °. The residue is stirred with 200 parts of xylene and poured into the suspension heated to 100-110 ° over the course of time a warm solution of 3.3 parts of sulfur in 1/10 parts of xylene is added dropwise over a period of 2 hours.The mixture is stirred at 120-125 ° for 2 hours until it is completely discolored, then cooled

309326/1198

226234Q ₀

.Case I5O-3352

Sucked off precipitate, washed with methyl alcohol, then with water and dried. After recrystallization from trichlorobenzene with the addition of a small amount of fuller's earth, the compound of the formula (1) is obtained in the form of pale yellow crystals with a melting point of 253-256 ⁰ .

Method c

By reacting a solution of 26.7 parts of the phosphonium salt of formula (5) in 600 parts of dry dimethylformamide under nitrogen with 10.5 parts of 4-cyano-4'-biphenylaldehyde in the presence of 3.0 parts of sodium methylate at 70-80 °, the compound is likewise obtained of formula (1).

The 4-cyano-V-biphenylaldehyde with a melting point of 157 ° -8 ° can be found in high yield by hydrolysis of the urotropin salt of 4-cyano-V- (bromomethyi) -biphenyl Prepare [Formula (4)] "in boiling aqueous acetic acid (Sommelet reaction).

Method d

A solution of 27 * 2 parts of 4- (bromomethyl) »4'-cyanobiphenyl [formula (4)] in 300 parts of dry xylene is added dropwise to 20 parts of triethyl phosphite at 140 ° in the course of about 30 minutes. After completion of the addition, the xylene and the formed during the reaction Aäthyl »bromide is distilled off over a column and the clear solution kept for 14 hours at 190 ^0th After cooling to 60 °, the excess triethyl phosphite is removed in a high vacuum 'at 0.01 mm * The crude diethyl phosphonate (31.2 parts) is under nitrogen and'

309826/1198

C ase 1 50-

Exclusion of moisture with 320 parts of dimethylformamide and 21 parts 4-cyano-4'-biphenylaldehyde is added and the mixture is heated to about 40 °. In the resulting clear solution becomes, with vigorous stirring, a freshly prepared solution of 2.6 parts of sodium in ^ O parts Methyl alcohol was added dropwise within 15 minutes. After the addition has ended, the brownish-yellow suspension becomes 30 minutes at 40 ° and 3 Stirred for hours at 80 °. After cooling, the reaction mixture is diluted with 640 parts of methyl alcohol and the precipitate which has separated out is diluted Sucked off, washed with water and dried. Obtained by recrystallization from dimethylformamide or trichlorobenzene the compound of the formula (1) is purely analytical. It melts at 253-256 °.

Method e ι

24.5 parts of p, p'-bis-f4-bromophenyl -) - stilbene and 13.4 parts of copper-I-cyanide are refluxed for 16 hours in 200 parts by volume of quinoline. After cooling the reaction mixture, one obtains a dark brown crystal oil, from which by suction and post-treatment of the filter residue with approx. 100 parts by volume each cold, concentrated hydrochloric acid, water, concentrated ammonia, water and finally acetone after drying light brown powder is obtained. This is solved in 2000 parts by volume 1,2,4-trichlorobenzene and boils after adding a few parts Fuller's earth reflux the mixture for another 10-20 minutes. After the hot filtration, the hot solution can be removed by briefly Bring it to the boil with a few parts by weight of basic aluminum oxide of activity level II, along with hot filtration, to lighten it even further.

309826/1198

- Case 150-3,553

After it has cooled down, the long, skewered för * - Substance that has crystallized out with pale yellow needles is washed off with cold methanol and, after drying in vacuo, receives about 16 parts by weight (80 ^ d.Th.) of crude product. After further recrystallization (twice from trichlorobenzene or dimethylformamide) a pale yellow compound that melts at 252-255 ° is obtained in good yield., which corresponds to the formula (1). The solution to this connection in 1,2,4-trichlorobenzene is -colorless, fluoresces strongly violet and shows a UV absorption maximum at 150-350 nm (extink-

tion - 6 .10). .

The p, p ^? -Bis- (4-bromophenyl) -stilbene of the formula

(7) can ζ, B. can be produced by the following methods.

With the exclusion of moisture and atmospheric oxygen, 13/1 parts of triphenyiphosphine are added to a solution of 16.3 parts of 4-bronchi-4'- (bromomethyl) -biphenyl in 400 parts of dimethylformamide at 60-65 °. It is stirred for 3 hours at 80 °, the clear, colorless solution brings back on oO ^ö and dropwise within 15 min, a freshly prepared solution of 1.3 parts of sodium in 25 parts of methyl alcohol, a * The deep orange-red suspension is 30 minutes at 80 ° stirred and then in a water jet vacuum at. Evaporated to dryness at 50 °. The residue is stirred with 200 parts of xylene, and in the course of the suspension heated to 100-110 °

309.828 / 1198

I 50 -3> j2

a warm solution of 3.3 parts of sulfur in 130 parts of xylene was added dropwise over 2 hours. The mixture becomes completely discolored Stirred for 2 hours at 120-125 °. The fancy yellow one After cooling to room temperature, the precipitate is filtered off with suction, washed with methyl alcohol and water and dried. The compound of the formula (7) with a melting point of 3 ^ 6-352 ° is obtained in good yield, which is sufficiently pure for further processing. By recrystallization from 1,2,4-trichlorobenzene with the addition of a small amount The product can be cleaned with fuller's earth. Light yellow crystals from Schinp are obtained. 356-358 °.

The 4-bromo-4 '- (bromomethyl) -biphenyl (of m.p. 92-9 °) can e.g. by side chain bromination of 4-bromo-4'-methylbiphenyl [formula (2) j are produced in boiling chlorobenzene under UV irradiation.

By reacting the solution obtained from 16.3 parts of 4-bromo- ^J l -'- (bromomethyI) -biphenyl and 13 * 1 parts of triphonylphosphine in high parts of dimethylformamide (see above) with 13, 1 part of ^ -Bromo-M -'- biphenylaidehyd in the presence of 3.0 parts of Natriurnmethyl ™ at at 70-30 ° is also obtained in good yield to the compound of the formula (7) (light yellow powder of melting point 3 ^ 8-356 °). The i * -Bromo-V ~ diphenylaldehyde of m.p. 137-1 ^ 0 ° can be produced in a simple manner by hydrolysis of the Urotropinsalaes from H-Bron-4 * - (bromomethyl) -biphenyl in boiling aqueous acetic acid (Somnielet reaction) .

By boiling a 20% solution of fumaric acid bis (v-bromodiphenyl-4) ester for 50 hours, which of the formula

309826/1198

- 50- - Ca se

% 4

θ V (bV ^ooc —Ο * ca_JOO_ / oy / QV_Br (8)

corresponds to, in Dowtherm A (mixture of approx. 78 % diphenyl ether and approx. 22 $ diphenyl) under nitrogen and purification of the cold sucked off crude product by briefly boiling with a little dimethylformamide and by recrystallization of the hot sucked off filter. residue with 1,2,4-trichlorobenzene using some bleaching earth, the compound of formula (7) is obtained in the form of light yellow crystals. It is analytically pure and melts at 356-358 °.

The fumaric acid diaryl ester of the formula (8) is conveniently prepared by heating for several hours a solution of 2 mol of 4 ^T- bromo-4-hydroxydiphenyl (lit. Hours at 150 ⁰ and a further 4 hours at reflux temperature) and recrystallization of the substance which has been sucked off after cooling with chlorobenzene using fuller's earth. Yellow needles are obtained which melt at 256-259 °. The substance is sufficiently pure for further processing.

The stilbene compound of the formula (7) may also consist of 2 moles of 4 ~ ^f -Brorn diphenylaldehyd-4 by benzoin condensation, followed by reduction to the corresponding deoxybenzoin in addition to thermal treatment with aluminum! Soprcpylat according to G. K. Drefahl and Thalmann * J.prakt. Chem., 4th series, 2O, 60 (1963) if the equivalent amount of 4'-bromo-diphenylaldehyde-4 is used instead of p-terphenylaldehyde-4, intermediate compounds of the following

Formulas ■ '-'-- "'

309826/1198

OH 0

2252340

^Br - ^ p) - ^ (o) - f - c - <O> - ^) - Bn

150-3355

and Br

(U)

be obtained

or

by reacting 2 moles of 4'-bromo-diphenylaldehyde-4 with 1 mole Hydrazine to aldazine of the formula

O / CH = NN = CH (O) (θ) ^Br C ¹² )

and by thermal treatment of this compound in bowtherm A. with the same reaction conditions as in the thermal treatment of the fumaric acid ester of the formula (8), (cf. also Bull. Soc. Chim. France 1970 (2), pages 525-527), or

by splitting off hydrogen bromide with simultaneous rearrangement from the compound of the formula

CH ₂ Br

in boiling ethylene glycol {H.Sieber. Liebia Ann. Chem. 730, 31-46 (1969) 1 or in amyl alcohol [Al-Attar and R. Wizinger, HeIv. 46,

309826/1198

-52 - ■■. * ■ Cp.se 150-3352

1286 (1963); the l, l-diaryl-2-bromoethane of the formula. (13) is off 4-bromodiphenyl and bromoacetaldehyde! Accessible J,

or by dehalogenation of the compound of the formula

CH-CH
jt

Br Br

(14)

with reducing metals (e.g. zinc) or copper-I compounds (Soc. 194 ^, 1; Referat .C. 194j II, 7I5) or triphenylphosphine

[j. Org. Formerly Jo, 2.377-9 (1971) 1 '

When the compound of formula (14) under appropriate conditions reacted with excess copper cyanide, however also removed the two bromine atoms bound to benzene nuclei and replaced by cyano groups. In this case, the compound of the formula (1) (^ method e-bis) is obtained directly. ".

Mf. Chode f

23.5 parts by weight the formula

Fumaric acid bis (4'cyanediphenyl-4-) ester

(O) 00C-CH = CH-C00w_ / Q

-CN (15)

are dissolved hot in 70 parts by volume of Dowtherrn A (mixture of approx. 78 % Bffenyl ether and approx. 22 % diphenyl), the solution is refluxed under nitrogen for 5.0 hours (temperature approx. 250 °). After cooling, the crystallized crude product is the same

3 0 9Π2Β / 1138 -

Case 1 50-3352

Way as in method a) recrystallize. The connection obtained corresponds to formula (1) and shows the properties specified for method a).

The preparation of fumaric acid esters of formula (15) is carried out analogously as in the reaction of V-Bromo-4-hydroxydiphenyl to fumaric acid, esters of the formula (8) of Λ '-cyano-4-hydroxydiphenyl (Preparation of the bromo derivative by reaction with CuCN in dimethylformamide) and fumaric acid dichloro, along with recrystallization in benzene using fuller's earth, a beige colored powder with a melting point of 260-270 ° is obtained, which is sufficiently pure for further processing.

Example 2

Preparation of the compound of formula

18.9 parts of the compound of formula

(16)

(17)

20.0 parts of p-terphenylaldehydanil and 20.1 parts of potassium tert-butoxide in 90 parts by volume of dimethylformamide with stirring and nitrogen heated atmosphere to 90 ° within 30 minutes and during Maintained at 90-93 ° for 1 hour.

309826/1198

Case 150-3 ^ 52

The reaction mixture is then cooled to 10-20 ° and first 630 parts of water and then 540 parts by volume of 10% hydrochloric acid are added. The precipitate is then filtered off _{with suction 4} , washed with water and dried. ■ ·

After recrystallization from o-dichlorobenzene with the addition of fuller's earth the compound of the formula (16) is obtained in good yield melting point above 350 °, which in trichlorobenzene is blue-violet fluoresces. ■ ■

X., (Trichlorobenzene) - 375 nm..

Example 3 '

Is used in Example 2 instead of 18.9 parts of the compound of the formula (1?) 2 ^, 0 parts of the compound of the formula

(18)

and if you proceed otherwise as stated there, you get in the same way good yield the compound of the formula

(Trichlorobenzene): 379 nm

which purified from tilmethylformamide, a melting point of 133 ° has (light yellow powder),

309828/1198. '

Case

example

Preparation of the compound of formula

»^ Parts of the compound of the formula

(21)

and 28.0 parts of triphenylphosphine in 500 parts by volume of dimethylformamide are heated at 80 ° for 1 hour while stirring. laugh During this time, 26 »O parts of p-terphenylaldehyde are added to the clear solution. then 11.0 parts of sodium methoxide were added * Subsequently the mixture will be shaken at 80 ° for a further jj hours * then cooled to 10-20 °. The precipitate is filtered off, getiOcIcmet and from chlorobenzene, with the addition of fuller's earth * umk55 * isallized. Ir. good yield is the compound of formula (2Q) Melting point 320 ° and Λ (trichlorobenzene): 363 nra ..

The compound of the formula (21) can be prepared as follows

11.3 'parts of sodium are taking. Zealous In 2 © ¹ © part »Aetlijlalkofaol solved · tmdf at ltevmtem && rm, twt ' with · ψ $, 2. Ämyliiltrit slowly · added., Bas · MeaktJ © es ^; ge «i3; € i! _: wirti ίΙιιιϊβ * t * f & -3 ^φ cooled and at this temperature 63.7 parts of ^ - acetophenone are gradually added dropwise. Mn η stirs 2 ^l \ hours - at O ^{1 -}

then a further 24 hours at room temperature, the precipitate formed is filtered off with suction, washed thoroughly with ether and dried him. The product thus obtained is then dissolved in 800 parts of ice water, the solution obtained is decolorized with activated charcoal and finally 80 parts of glacial acetic acid are slowly added with vigorous stirring. A white precipitate separates out, which is suction filtered, neutral washed and dried. The compound of the formula is obtained in good yield

CH (CjS -CO-CH = NOH. (22)

with melting point 108-109 °, which without additional. Cleaning continues is implemented. -

20.8 parts of the compound of the formula (22) are dissolved in 185 parts of methanol, and a solution of 2.7 parts of glacial acetic acid in 2/7 parts of water is added. 5.7 parts of pheriylhydrazine are then slowly added dropwise and the mixture is stirred for a further hour. The reaction mixture is then completely concentrated in vacuo and the dry crude product obtained is suspended in II6 parts of glacial acetic acid. The suspension obtained in this way is gradually added to 250 parts of molten urea with stirring at 150 ° and the reaction mixture is stirred for a further 3 hours at 175 °. It is then cooled to 140 ° and 400 parts of 2N sodium hydroxide solution are gradually added. The reaction mixture is finally cooled to 0-5 ° and the resulting precipitate is filtered off with suction, washed neutral with water and dried.

30 9 8 26/119 8

Case

After recrystallization from petroleum ether, the compound of the formula is obtained

which has a melting point of 66-68 °.

20.0 parts of the compound of formula (23), 15.2 parts of N-Bromsuccini- mid uhd- 0.2 parts of benzoyl peroxide in 85 parts by volume of carbon tetrachloride are heated with tubes for 6 hours under reflux. The reaction mixture is then cooled, the precipitate is filtered off with suction and the filtrate is strongly concentrated in vacuo, the compound of the formula (21) precipitating out. Purified from ligroin, it has a melting point of 121-122 °; however, the crude product is sufficiently pure for the next conversion.

Example 5

Preparation of the compound of formula

(24)

Is used in the example k instead of Jl, ¹ + parts of the compound of formula (21) 35.3 parts of the compound of formula

309826/1198

- Case 150-3352

35 - ■■■. ' ■

and proceed as indicated there> so; the compound of the formula (24) [A. (Trichlorobenzene) -t57O rim-J, which after cleaning from dimethylformamide under. Addition: before decolorizing, charcoal has a melting point of 267-268 °.

The compound of formula (25) can be prepared as follows:

100.0 parts ^ -Cjran - ^ - methyl-l-arainob-e-nzol. (from the corresponding Ni trover binding by reduction according to Bechamp; fetar.-g.es shares). in 320 parts by volume of glacial vinegar: dissolved and in a mixture of 42> 0 Parts by volume of sulfuric acid and 6 parts by volume · Ice: within JO minutes dripped in. “Regarding the reaction according to hurry. w-i, rd then a solution of 5'4-jr.ö parts of sodium nitrite, added dropwise in 114 parts of water and "the obtained di azo solution; becomes after j5Q minutes; further stirred.

70.0 parts of Iscnitrosqaeeton in J&Q. Files. Water 'will .zuerst with a solution vanv _£>: 9 parts: Ifetrium; Suo: .fi.t in: 76 parts · water and a solution: from 19- parts Kup.fea sulfate in: Jq- parts water . added ^ then ^{filtered to '0 a} . and - with the ma ^ olösusig: TersetÄt .: The mixture: is then: ssends 12 hours, left to stand ^ dtetr sehlag. is then suctioned off, washed out with water; l, igr ^: oiri; receive; raani'in> well he · 'exploit ^' diie

- Case 150-3352

Ho

NOH (-26)

of melting point 185-186 ⁰ .

71 * 3 parts of the compound of formula (26) in ΙΟβΟ y Methanol is mixed hot with 151 * 2 parts by volume of acetic acid Ii1, then the mixture is briefly boiled and afterwards with 38 * 1 parts Phenylhydrazine slowly added.

The suspension is then refluxed for a further 2 hours, then cooled; the precipitate sucked off and dried. The compound of the formula is obtained in very good yield

with a melting point of 248 ° (from chlorobenzene).

73.0 parts of the compound of formula (27) in 275 parts by volume of dimethylformamide are added to 300 parts by volume of acetic anhydride and 200 parts by volume of pyridine and heated over 1.5 hours to 8Q ^P and sehajten for further 2 hours at this temperature. Afterwards the mixture is maintained for 4 hours at 1QQ ^P, then heated to boiling and held for 30 minutes at reflux.

309 826/11 ff

Case 1 ^ 0-3352

The 'reaction mass is then cooled and in 2000 parts of water poured, the precipitate is finally filtered off with suction and dried. After recrystallization from methanol is obtained in very good Yield the compound of formula

(28)

from the melting point

The compound of formula (28) is then combined with N-bromosuocinimide the compound of formula (25) implemented analogously to the information for the compound of the formula (23) »Purified from ligroin, shows the Compound of formula (25) has a melting point of 147-148 °. ·

Example 6

Preparation of the compound of formula

H = CH

20.0 parts of the compound of the formula

(29)

CH ₂ Br

(30)

30 98 26/1198

Λ. , Case I3O-3352

and 15.3 parts of triphenylphosphine in 480 parts by volume of dimethylformamide are heated with stirring and under a nitrogen atmosphere for 3 hours at 80 °.

12.4 parts of the compound of the formula are then added to the clear solution

CHO

(3D

and 6.0 parts of sodium methylate are added and the mixture is additionally heated for 4 hours at c0 °. After cooling, the precipitate is filtered off with suction, washed with water and dried. Recrystallization from chlorobenzene with the addition of fuller's earth gives the compound of the formula (29) in good yield, which melts above 350 °; A _M (dimethyl sulfoxide): 375 nm.

The compound of the formula (30) can be selected from the compound of the formula

(32)

by bromination with N-bromosuccinimide, analogous to the information for the Compound of formula (23) can be produced and shows a Melting point of 195-197 ° (from chlorobenzene).

The compound of formula (32) can be prepared as follows:

309826/1198

- ■ gases 150-3352

- ■■■ ".

Parts of the compound of the formula

OQH (33)

and 19.4 parts of o-aminophenol ± _n 284 parts of polyphosphoric acid are added with stirring and nitrogen atmosphere. heated to 110 °, kept at this temperature for 10 minutes, then heated to 210 ° and stirred for 3 hours at 210-220 °. The temperature is then allowed to drop to about 100 ° and the mixture is poured into 140 ° Q. Parts of ice water .. The precipitate is then filtered off with suction, washed neutral with 10% soda solution, then with water and dried.

The compound of the formula (32), which is used without additional purification, is obtained in a practical, quantitative yield. Recrystallized from ethanol, the compound of the formula (32) has a melting point of 169-1? O ^p ,

The connection of the formula .3I) kapn.- can be established as follows: 2Q parts of the compound 'of the formula' "- '"' ■■

will be in 5QQ. Divide ^ hiorbenzoi un% er Rüipe-n, and then uf ^ ter · | JVWBe; g * rahl
in ißQ parts ghiorbqviz.ql \

Then v / ir.d · es' untöT ¹ tube χχάά · another

cooked until the evolution of hydrogen bromide; subsides (5-6 hours), The reaction mixture is then cooled, the precipitate is filtered off with suction, washed cold with chlorobenzene and dried. You get the compound of the formula in very good yield

05),

which., purified from chlorobenzene, has a melting point of 168 ~ 109 ° having.

The compound of formula (31) is finally obtained from the compound of formula (35) by Sommelet reaction ^ and has a melting point of 16O ⁰ to I61.

Example 7

Preparation of the compound of formula

= CH

OJ (36}

Analogously to the information in Example 1, the compound of the formula (30) by reacting with triphenylphosphine and exchanging the bread anions through the periodate anion in the compound of the

9820 / 11SS

- ¥¥ _ caso 15 0-3352

converted, which then gives the compound of formula (36) by reaction with sodium ethylate. Purified from dimethylformamide, shows the compound of the formula (36) .a melting point above 350 °; ^^ trichlorobenzene): 372 nm. - · ■

Example 8

Preparation of the compound of formula

O V-CH = CH (Ο

Analogously to the information in Examples 1 and 7>, the compound of the formula becomes · ■ · ■ / ■ _ -.- "■ -.

O9)

the compound of formula (38) prepared which has a melting point above 350 °; / ^ (Trichlorobenzene): 375 no. ^}

The compound of the formula (39) can be derived from. of the compound äev formula

O) (O) - CH ₀ Br

O / ^ HOh-cH,

are prepared, analogously to the information, for the compound of the formula (23). It shows a melting point of 205-206 ° (from ethanol). the Compound of formula. ■ (40) is produced as follows:

309826 / 1T98

C ase 150- 5352

16.5 parts of a-hydroxy-S-tert-butyl-1-aminobehzol, 21.2 parts of the compound of the formula (33), 2.0 parts of boric acid and 8.5 parts of piperidine in 14o parts by volume 1.2, ^{4-Trichlorobenzene is heated to 160 p} within 1 hour with stirring in a nitrogen atmosphere, kept at 160-170 ° for 1 hour, then heated to 200 ° over 1 hour, stirred at 210 ° for 1 hour and finally refluxed for 4 hours. The water that forms is removed azeotropically. After cooling, parts by volume of isopropyl alcohol are added to the reaction mixture; stirring is continued for 30 minutes and the precipitate is filtered off with suction and dried. After recrystallization from ethanol, the compound of the formula (40) with a melting point of 167-168 ° is obtained in very good yield.

Example 9

Analogously to the information in Examples 1 and 7, all of the compound the formula

(41)

the compound of formula

-λ f ^

- 'S- *> -'

manufactured. The compound of the formula (41) can, starting from

the compound of the formula

309826/1198

150-3352

COGH-

analogous to the information for the compounds- (22) ,. (23) and (21) will.

Example 10 ■ '■ ■■ - - -. \:.

Analogously to the information in Examples 1 and 7, the compound becomes the formula '

(44)

with shrap. 223 °) the compound of the formula

[Sciimp .. over 360 °; λ max (CHCl) ί382 nmi obtained. The connection of the forms.! (4: 4,) can be produced by bromination of the corresponding methyl bond (Sehtnp, 215-216 °) ^! will be obtained by the chemical analysis of the compound of the formula (33), analogously to that described in HoIy. Chiriu Ae ta 50, 935 (1S ^ 7O ^: "& ^ very i flat .Process ^, -?.,>.." »,, .. ^,

3QS828 / MSS ■ '■ - ^: - = - ~ - ^ n

Ca;

Example 11

Analogously to the information in Example 5, the compound Af) V formula

= Cd

(Mp. 5ΟΟ-5Ο2 ⁰ ) from 2,4-dicyanobenzyl bromide and Dlphenyialdehyd be prepared. The 2,4-dicyanobenzyl bromide (melting point 106 °) can be obtained from 2,4-dicyantoluene (melting point 142-143 °) by bromination with bromine in chlorobenzene under UV radiation. The 2,4-dicyantoluene can be obtained from 3-cyano-4-methyl-1-aminobenzene by Sandrneyer's reaction.

Example 12

The compound is completely analogous to the compound of the formula (24) the formula

O) -

CH =

from the compound of the formula (25) and Dipheiiy.laldehyd hefgest-ellt Mp. 245-246 ° (from Cellosolve): absorption maximum in OiCl-, = j? oO n ", E-nissi ons maxi mum in CHCl-" 4 ^ 3 na "

Example , ... 13 'If one files> -3 instead of 2J in example 1, method f)

Case 150- 3352

Fumaric acid bis (4'-cyandiphenyl-4) ester of the formula (15) 28.2 parts of the fumaric acid ester of the formula

H ₅ C ₂ OOC— (O / \ Oy — 00C-CH = CH-C00— / O) - \ O / —COOC ₂ H (48)

used, one obtains after repeated recrystallization (1,2,4-tri chlorobenzene) using fuller's earth a yellow-green powder, which does not melt up to 350 °.

The compound obtained in analytically pure form corresponds to the formula

= cn— \ W ~ \ W — COOC ₂ H ₅ (49)

The solution of this compound in 1,2,4-trichlorobenzene is colorless, fluoresces strongly red-violet and shows a UV absorption maximum at 361 rinr (extinction = 5.6.10).

The fumaric acid ester of the formula (48) can be prepared from ethyl 4'-hydroxydiphenyl-4-carboxylate (accessible from 4'-cyano-4-hydroxydiphenyl by alcoholysis with ethyl alcohol and sulfuric acid) and furnaric acid dichloride in the same way as the fumaric acid esters of the formula (8) or of the formula (15) and prepared by recrystallization in Chlorobenzene can be purified using fuller's earth. Man you get a yellow crystal powder, which melts at 259-267 ° and is sufficiently pure for further processing.

Example 14. ■. λ

Analogous to the information in example 1, one can derive from the connection of the

309826/1198

Case 150-5352

formula

ίο

(50)

the compound of formula

obtain. The compound of the formula (50) can be obtained by bromination corresponding methyl compound of the formula

(52)

be prepared, which in turn from Methyl-IA ¹ -diphenyl - ^ - sulfone äurefnach Ber. 65 (1932), pp. 1382-7], analogously to that in J. Chem. Soc. London 1960, Hj p. 2508 can be obtained. Solutions of the compound of the formula (5 ¹ / in o-dichiorobenzene show a strong blue-violet fluorescence.

Example 15

Analogously to the information in Example 5, one can choose from the compound of the formula (25) and the equivalent amount of the compound of the formula

(53)

309826/1198

the compound of formula

(54)

^V C1

whose chlorobenzene solutions have a blue-violet fluorescence. The compound of the formula. (53) can e.g. be obtained according to the information in the ÜS patent specification 2 280 504 (cf. also B E III I ₃ 2091) ».

Example 16

If in example 1 (method e) instead of 24.5 part of the connection of the Formula (?) 26 parts of the compound of the formula

(55)

are used, one obtains in an analogous manner a light yellow ,, in Trichlorobenzene solution violet fluorescent compound of the formula

KC-

(56).

Slide Verblniiitog 'the Facmel (5 _£>}:
Connection of the formula

^; fflaTni ^: e.g.

Can? 3

CH ₂ Br

■ (57)

which by converting 3-f (Κρ. _γ6ο 318-323 °; Kp ^ 165-170 ⁰ ; n ^ ⁵ = l, 6l5Oi at, iS§Hffeein E IXX, Volume V, S.I800, · J Am.Chem.Soc. ^ (1933), 1212-1217 and «j8 (1936), 12 ^ 9) with excess paraformaldehyde and excess sodium bromide in a sulfuric acid-glacial acetic acid mixture at 100 ^{6 in} addition to the usual work-up is accessible in good yield and as a crude product is used, with the stoichiometric amount of tripene phosphine and exchange of the bromine ion by the periodate anion 3WF compound of the formula

which is implemented analogously to Example 7 with Ifs.tr iumS thy lat.

Application example A

2 parts of the compound of formula (1) are mixed with 2 parts of one high sulphonated castor ice, 8 'files diootylphenylpolyglykollitheroxyessigsaurem Sodium, which contains 4Ό ethene oxygruppeη in the molecule / and 80 parts of water and processed the mixture in a ■■ 5 firing device, e.g. in a

0 _r 5 ^ -2 I *, fairy bears

100 parts of a polyester fabric (polyethylene terephthalate) »ground at 50 ° in a bath with the following composition:

3000 parts of water

15 parts of a commercial carrier, e.g.

ortho-dichlorobenzene, 2 parts of the dispersion described above. .

Bring the bath to the boil within 30 minutes, leave it for while 45 minutes at the boiling point under reflux and then treated the tissue at 70 ° in a bath containing 1.5 g / l octyl

s

contains phenyl decaglycol ether (liquor length: 1: 40, duration: 10 minutes ). It is then taken out, rinsed warm and dried. The polyester fabric treated in this way is heavily lightened. If one works in closed apparatus at 120-130 °, one achieves without Addition of a carrier similar white effects.

To vfiendunr; s example B

A cotton / polyester mixed fabric, for example cotton / polyethylene terephthalate, is impregnated at room temperature in a padder with a liquor which contains 20 parts of the optical brightener dispersion described in Application Example A in 1000 parts by volume. It is squeezed off to 80% liquid absorption, dried for 30 minutes at 60 ° and thermosolated for 1 "minute at 200 °. In this way, the fabric is strongly lightened, similarly to the method described in application example A instead of the mixed fabric, a pure polyester fabric

this is also lightened

(Dacron, Terylene, Diolene, etc.), so we do

-30 & 826 / 1T98

226234Q

Oa se 1 ^ Q-

like the mixed fabric.

Application example C

100 parts of polyester fabric, for example polyethylene terephthalate, are treated in a bath for 1.5 hours at 90-95 °, the JOOO 'parts of water, 6 parts of 85% formic acid, 6 parts of 80 % 1 total sodium chlorite, 5 parts of a carrier, for example contains a trichlorobenzene mixture and 2 parts of the dispersion described in application example A ;. The fabric is then washed, rinsed and dried. It then has a higher degree of whiteness than a fabric which has been bleached comparatively without the addition of the compound of the formula (1) under otherwise identical conditions.

Application example D

50 parts of polyester fabric are briefly removed in a mixture of 250 volumes of trichlorethylene and 250 parts by volume of chlorobenzene in which 0.2 parts of the compound of formula (1) are dissolved. The excess solvent is spun off (approx. 100 $ solvent absorption) and the fabric is dried at 60 ° in a vacuum and then treated for 15 minutes with steam at 120 to -50 °. The polyester fabric treated in this way has a significantly whiter appearance than an identical fabric treated comparatively - as indicated above, but without the addition of brighteners.

If you use a mixed fabric instead of the polyester fabric Cotton-polyester, ^ .B-Baurnvvolle-rDiolerfy so, is also obtained an effective brightening des'e töetil "''" '

309826/1198

22 & Z340

ease 150-3552

E :

2.0 parts of polyethylene terephthalate are melted in a container in a nitrogen atmosphere at '2 "So- ⁰ ' and 0.04 parts of the compound of the formula (1.) are added. The brightening agent melts at this temperature and is stirred into the polyester, Then 4 parts of titanium dioxide are added as a matting agent and the whole mass is stirred again until a homogeneous mixture is obtained. This is then pressed through a spinneret and the thread produced is first cooled by a water jet or air then stretched and wound on spools in the usual? manner.

Products made from these fibers have a significantly higher degree of whiteness than with the same process, but without the addition of the brightening agent.

Is used in place of the connection; of the formula ζ%} - the connection of the formula (% 5) so one gives a-ri äfenCLictten ^ Weisseffefct.

Application example · F. : ■ _: ■. .- ,. "· ^,.... -

In a stainless steel autoclave; Sta: hp. _r; ams with a descending Jiü & leiv · warmed, all together lOOO ^ Tsile Mmethylt ^ repteth ^ at _i . ^^ ^;

0> 55 parts ManganaeetiEtt ^ Ö> 1: S TJeJIe

0y ~ $ parts / the ¹ misalignment. äev ifeEmei (!} * - © te! JS tting, äes iJietEiariioOlH fe © g; innt: feef "estwa ^ l ^ ÖP It sM '2: 1 / P ^: ßittiradem» Df e ^{; Ι} Ατη · ρ «ratlin sfeeigt' -ge ^ eia "" Ariele '&&& tiü

BATH

885 * · * · * "then are k skins titanium dioxide and 0 * 3 phosphoric zu'der melt lowers the pressure

bevel below 1 mm and keep the temperature at ■ $$ &% The desired degree of polymerization has been achieved, Da «so

Pol | mere is made with einito using a known method

from 8-5 atmospheres (inert gas) spun into threads «UIe held polyester threads have a high good wash and lightfast 1st.

Application example G ■. ■ · ■■

500.0 parts of polyamide chips made of / -Caprolactam »dioxide and 0.1 part of the compound of the formula (20) are intimately mixed in a mixer and then melted in an autoclave at 230 ° to 260 ° with the exclusion of oxygen With the help of nitrogen pressed through a spinneret *. the cooled filament is stretched to 400% and then wound onto a spinning bobbin,

The polyamide fiber produced in this way is characterized by a very high degree of catfish. Instead of the compound of the formula (20), the compound of the formula ( ^J * 2) or the compound of the formula is used with equal success

Application example H

1000 parts of Caprolaetam, JO parts of water and 0.8 parts of brightening agent of formula (20) k in RUhrautoklav hours Ü40 ° (under pressure), then heated for 1 hour under relaxation * The polyamide melt thus prepared is slit Elrie ^p

309826 / iill

- Ce se ? 5 0-3352

in sand form quenched in water, carved and dried. The raw material has a greatly increased degree of whiteness compared to a correspondingly manufactured blind product. In the same way can the compound of the formula (1) can also be used. .

Application example. J.

Polypropylene granulate matted with titanium dioxide is powdered in a mixer with 0.01 to 0.05 % of its weight of the compound of formula (16) and ^{melted in an apparatus customary for the shrink spinning process at 3IQ 0} in a nitrogen atmosphere and spun into threads. ·

The threads produced in this way are hot stretched in the Zv / eistufenverfahren. They show a much higher degree of catfish than comparatively produced without the addition of a brightener. Similar white effects can be obtained if, in this example, instead of the compound of the formula (ΐβ), the compounds of the formulas (19) and,. (20) are used. .

Application example K

A solution-of 200.0 parts of polyvinyl chloride and 0.04 parts of the Compound of formula (1) in methylene chloride is made by the wet spinning process spun into threads. A brilliant white fiber of good lightfastness is obtained. Similar to the connection of the Formula (1) are also suitable for this purpose, the compounds of formulas (46) and (24).

ν 309826/1198

Application lighting game L

200.0 parts of polypropylene granules are in a .Mischapparat with Ο, ΟΛ.Share the compound of the formula (19) powdered on the rolling mill Processed at 14O to 220 ° and either pressed into / panels or regranulated and pressed into pellets in an injection molding process

The products obtained have a significantly improved degree of whiteness compared to those produced without the addition of brighteners. Used if instead of the compound of the formula (19) one of the compounds of the formulas (17) or (38) is obtained, similar white effects are obtained »

Application example M

100.0 parts of polyester granulate are powdered with 0..02 parts of the compound of the formula (1) in a mixer and subjected to the injection molding process. The products obtained have an improved appearance compared to those produced without the addition of brighteners. If, in this example, the polyester granulate is replaced by granulates of other materials, such as polyamide, polystyrene, polyethylene or cellulose acetate, then similarly brightened products are obtained; ^{likewise if the compound of the formula (;} I5) is used instead of the compound of the formula (1).

Application example ^?

100.0 parts of a polyvinyl chloride composition consisting of 65 parts of polyvinyl chloride, 35 parts of a plasticizer, e.g. diootyl phthalate and 2 i> based on the polymer of a stabilizer, is mixed with 0.01 to 0.05 parts of the compound of the formula (20), 3 to 6

309826/1198

Minutes at 16 $ Ms l8§® aiii * the rolling mill un-belted uik * pulled out to traps »For the production of opaque I? Oiien. 4er before det * V ^ i \ arbeiiyung 2 ^% titanium dioxide ^ g ^ miseht;

The wrinkles created in this way: have a

about those which are made without any brightening agent

Application example Q

Mixing 2 ^parts;: '^ dey compounds eggs _FQrme; 1 (1) with 2 parts of a highly sulfonated castor oil and 8 parts of octylphenyl polyglycol ether oxyacetic acid sodium which contains no ether groups. contains in the molecule, and 80 parts Viasser and processed the mixture in a grinding apparatus *, for example in a sand mill, until the particle size of the main amount is 0.5-2 ^.

A polyester fabric, fc.B. ähs polyethylene terephthalate, is at Skin temperature with a liquor foularcUert in 1000 parts Water, 20 parts of the dispersion prepared according to the above procedure contains, the active substance of which corresponds to Fovmel (1).

It is squeezed to 80 % liquid absorption. 50, dried minutes at 60 ° and thermosolated for 1 minute at 2? 0 °. In this way, the tissue is lightened with a strong reddish tinge. Instead of this polyester fabric, a mixed fabric made of 67 parts of polyethylene terephthalate and 3j5 parts of cotton or a fabric can be used. A differently composed polyester (e.g. 1, ^ - dimethylocyclohexane terephthalate) can be used.

ORIGINAL

Claims (1)

P a t ent claims eh each of the symbols R _pf wherein each of the symbols R ₁ and R _{r is} hydrogen, NitrlL pd ^ r J .- *! Contains carbon atoms in linear alkyl ^ R ₆ and R ^ hydrogen, one of the following substituents 1 * order: Fialof-en ,,. 1-8 carbon atoms containing alkyl or alkoxy or 3-8 ^f Alkenyl containing carbon atoms or one of the following. Second order substituents: -CN, -COOR ', -CONR ¹ R ", - ' ¹ ' gR "or SO ₂ R ', each of the symbols R and R ₇ hydrogen, one of the stated substituents of the 1st or 2nd order or one of the heterocycles of the following formulas 309826/1198 R ^{1 is} hydrogen, alkyl containing 1-22 carbon atoms, hydroxyalkyl containing 2-4 carbon atoms or optionally methyl- or chloro-substituted phenyl * R ^|: Hydrogen, alkyl containing 1-8 carbon atoms or hydroxyalkyl containing £ -4 carbon atoms, - or R "and R ¹ together with the adjacent nitrogen atom form one Pyrrolidine, piperidine > piperazine or morpholine ring, . ■ '. "■ - ■' ■■ '■■ ·"' ■ .- R ¹ "'optionally methyl- or chloro-substituted Phenyl,. R "" alkyl containing 1-4 carbon atoms or optionally methyl- or chloro-substituted phenyl, χ -0-, -S- -NH- or -NR "" ¹ -, ■ R ⁱⁿ "alkyl containing 1-4 carbon atoms or 2-4 Hydroxyalkyl containing carbon atoms, A and A if X -0-. means, optionally by chlorine or 1-4 Carbon atom-containing alkyl or alkoxy-substituted phenyl or, when X denotes -0-, -S- or -NR '"" -, a fused naphthalene nucleus or a fused alkyl optionally containing 1-8 carbon atoms by fluorine, chlorine, nitrile and / or Alkoxy substituted ben- 309826/1198 Case .150-3352 zolring, A, phenyl optionally substituted by one of the abovementioned substituents of the 1st order or non-heterocyclic substituents of the 2nd order, A ₁ , hydrogen or methyl, ρ is a whole number from 1 to 3 and q is an integer from 1 to 3, the sum p + q is at least 3, the sum of p +. qund the number of substituents of the 2nd order present in the molecule at least 5 and, if only one of the substituents R-. and R " 3 7 is a keterocycle, either the number e p + q is at least 4 and / or at least two further non-heterocyclic substituents of the 2nd order are present in the molecule. 2. stilbene compounds of the formula (I) according to claim 1, wherein at least one of the substituents R ₁ , R, R ₅ and R _{7 is} a second order substituent. . Stilbene compounds of the formula (I) according to Claim 1, in which the substituents R ₂ , R ₁ ^, R ₆ and Rg are hydrogen or substituents of the first order. . Stilbene compounds of formula (I) according to Claim 2, in which R ₃ , R ₁ ^, Rg and Rq are hydrogen. 309826/1198 . ■■ .J ■ Case 5. stilbene compounds according to claim I, of the formula (XVI) where leides eier symbols ^ and R ₁ hydrogen, methyl or -CM, each of the. .... Symbols R, ^ and R 'hydrogen or a nicl ^ t .. _: ■, .. ■ heterocyclic substituent 2nd order ,, preferably -GNj an alkyl or phenylsulfone group.: ■ ".... or a Ca.rbonsaurea.mid- or ester group ₃ _, and each of the symbols. R- .. _2> R, ^ R ^ and Ro have a substituent means, 1st order or preferably hydrogen where the molecule has 2 to k substituents of the 2nd order contains Siilbenverbiiidungen according to claim * 1 of the formula Wherein ₀₀ > ^{CH = CIT} 24 r-1 ■ s-1 (XVII) and R. Hydrogen, methyl or cyano, -. Preferably Hydrogen or cyan,. </, and RpQ. hydrogen or a substituent of the 1st order, preferably hydrogen, 309828/1198 BATH ORIGINAL if 2? 62340 ^ ^ each one of the hetero: · ^ c.llscrvjn sub? tidient 2nd order of the formula fa), (b) or (c), r is an integer from 1 to 3, preferably 1 or 2, and s is one an integer from 1 to 3, preferably 1 or 2, and the sum ims is 3 or 4. 7. stilbene compounds according to claim 1 of the formula CH = CH t-1 _J u-1 , (XVIII) wherein Π and R are hydrogen, -CN or methyl, preferably -CN or methyl,
^R 32 ^'R 36 ^{and R} 3V ^R ^ 3 ^Wass e ^r material or a substituent l.Ordnuri: - ;. preferably hydrogen, one of the symbols R and Ii _ψ one of the heterocycles ta] , (b) and ( _c ), the other of the symbols R_ and R ^ "hydrogen, a substituent 1st order or a non-heterocyclic 2nd order substituent, t is an integer from 1 to 3 and ^{u is} an integer from 1 to 3 mean, the sum t + u 3, 4 ^{oa «r} is 5, at least: - one of the substituents R - ,, R, _r and R _._.. or R_ "a not hsterocycli" 3 JL- 35 33 3f is a shear substituent of the 2nd order and, if the sum is Hu 3, at least two of the substituents R ₁ , R _vr and R ^ or W are not heterocyclic substituents of the 2nd order. 30 98 26/1198 BAD OBlGiNAU 8. A process for the preparation of the compounds of the formula (I) according to claim 1 characterized in that a compound of the formula. (II), p-1 wherein Y -CO-COOH or -CHO or a suitable functional. derivative the aldehyde group: means with a compound of the formula Z-CH (III), wherein Z is a sub-substituent activating the adjacent methylene group or, when Y is an aniide derivative of the aldehyde group and if there is no equally active or more active methyl is, also means hydrogen, converts and, if in the reaction product a substituent Z other than hydrogen is present, replaced by hydrogen, or in compounds the formula c (y _i ) ₂ -c (z ₁ ) ₂ - PI 309826/1 198 BATH ORIGINAL 2262540 Caao 150-3352 β » where each of the symbols Y and each 3-syrrbole 2. hydrogen, halogen " denotes a hydroxyl or acyloxy group or (Yt) ₂ ^un or (Ζ,)" each denotes doubly bonded oxygen, two of the substituents Y. and Z, optionally below simultaneous FIcduktion or oxidation and * if other substituents Y and / or Z are still present, these are replaced by H , or, if at least one NJ-trilgruppe is present in the compounds of formula (I), that one in one Compound of formula CH-CH- X) the substituents Rp, R ,, Rw, Rz-, R ,, and in which at least one of the symbols R 'to R ¹ η denotes halogen and the remaining symbols have the meaning given in formula (I) for R- to R ", the halogen is replaced by -CN, or in the compounds of the formula (I ), in which at least one for -CN, the latter is converted to a corresponding carboxamide, carboxylic acid ester or free carboxylic acid group or, if a heterocycle (a) is present in the end product of formula (I), that in compounds of formula (I) in which at least one of the substituents R , and R ,, a carboxylic acid, carboxylic acid ester or ÖarbonsaureamidgruppG, optionally after conversion to an enfätrespondclen carbo; acid halide group, this converts to a corresponding hot cycle (a), or, if the compounds of formula (I) are symmetrical . 3Q9826 / 1198 BAO ORiGINAt that-one -a: .compound of the formula wherein. W represents hydrogen, halogen or -E (aryl) ^ ^ l AnionM and Arj is vorzugsvieise monocyclic (optionally substituted phenyl) Uend / oäer reacted in alkaline medium just under oxidative conditions ^ n "wherein xvenn W stands for _halogen; the medium must be alkaline if W> stands for gas / hydrogen, one has to proceed in the presence of an oxidizing agent and if W- stands for, one has to proceed in the presence of a proton absorber and an oxidizing agent, or that one must proceed from symmetrical Compounds of the formula ^ Anion ' (VIT) οd ov the form "^ HNN-CH rrr 3098? Β / 1Ί98 BATH ORIGINAL - Case 150 3352 by thermal treatment in an inert atmosphere CO ₀ or, Np splits off. , 9. The compounds of the formula (V), 10. Process for the preparation of compounds of formula (V), thereby characterized in that one compounds of the formula ~ Y p-1 with compounds of the formula Z-C0 (X) converts or that one compounds of the formula ff. p-1 or (f Mr symmetrical pre-bonds of the formula (V) J of the formula 30982GM198 Case 150-3352 R '. Xl) CH ₂ -W (XU) P (q) -l- or the formula R ¹ C-CO-CH = CH-CO-C- p-1 (XIII) or the formula R \ -CH-N-M = CH p-1 Γ XIV) converts or that one compounds of the formula (XV) JP (q) ~ l with haloacetaldehyde or its functional derivatives and the reaction product is dehydrohalogenated and rearranged at the same time. 309826/1198 BATH ORIGINAL - fr? -. ^ iL_L: -tll52 ■ to 11. Verv / end of the compounds of formula (I) according to claim 1 as optical brighteners. 12. Verv / Endung according to claim 11, characterized in that one organic Optically brightens polymers. .13. Use according to claim 12, characterized in that one
lightens synthetic fiber-forming polymers. 14. Use according to claim Yj _1, characterized in that the compounds of the formula (I) are used as spinning mass whiteners. 15. Use according to claim l-'l-, characterized in that one polyester spinning mass brightens. 5700 / XD / SO 309826/1198